US3649719A - Phosphoric acid ester amidohalides - Google Patents
Phosphoric acid ester amidohalides Download PDFInfo
- Publication number
- US3649719A US3649719A US33862A US3649719DA US3649719A US 3649719 A US3649719 A US 3649719A US 33862 A US33862 A US 33862A US 3649719D A US3649719D A US 3649719DA US 3649719 A US3649719 A US 3649719A
- Authority
- US
- United States
- Prior art keywords
- formula
- compound
- hydrogen
- propen
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 150000003014 phosphoric acid esters Chemical class 0.000 title description 3
- 239000000460 chlorine Chemical group 0.000 abstract description 25
- 239000001257 hydrogen Substances 0.000 abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052801 chlorine Chemical group 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 8
- 239000000543 intermediate Substances 0.000 abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005864 Sulphur Chemical group 0.000 abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052794 bromium Inorganic materials 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 description 39
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 125000001309 chloro group Chemical group Cl* 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 3
- 241001143309 Acanthoscelides obtectus Species 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000000895 acaricidal effect Effects 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010410 dusting Methods 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- OWNZHTHZRZVKSQ-UHFFFAOYSA-N tribromo(sulfanylidene)-$l^{5}-phosphane Chemical compound BrP(Br)(Br)=S OWNZHTHZRZVKSQ-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 241001600407 Aphis <genus> Species 0.000 description 1
- 241001425390 Aphis fabae Species 0.000 description 1
- 241000239290 Araneae Species 0.000 description 1
- 241001127120 Dysdercus fasciatus Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- -1 N-n-propylphosphoramidothioate-dichloride Chemical compound 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 125000004803 chlorobenzyl group Chemical group 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- WVPKAWVFTPWPDB-UHFFFAOYSA-M dichlorophosphinate Chemical compound [O-]P(Cl)(Cl)=O WVPKAWVFTPWPDB-UHFFFAOYSA-M 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 150000003015 phosphoric acid halides Chemical class 0.000 description 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/26—Amides of acids of phosphorus containing P-halide groups
Definitions
- R is hydrogen or lower alkyl of 1 to 3 carbon atoms, R and R are lower alkyl of l to 5 carbon atoms,
- X is hydrogen or chlorine
- Y is oxygen or sulphur
- Z is chlorine or bromine.
- R is hydrogen or lower alkyl of l to 3 carbon atoms, R and R are lower alkyl of 1 to 5 carbon atoms, X is hydrogen or chlorine,
- Y is oxygen or sulphur
- Z is chlorine or bromine.
- the compounds of Formula I are useful as intermediates in the production of biocidally active phosphoric acid esters. Processes for the production of the compounds also form part of the present invention.
- R X, Y and Z have the above significance, with the equivalent amount of an amine of Formula III,
- R R NH III 7 wherein R and R have the above significance, 1n the presence of an acid acceptor, or
- an equivalent amount of an amine of Formula III in the presence of an acid acceptor e.g. triethylamine, trimethylamine, dimethyl aniline, diethyl aniline or sodium carbonate, is added at a temperature of to C., preferably at -l0 to room temperature, to a compound of Formula II in a solvent which is inert under the reaction conditions, e.g. an aromatic hydrocarbon such as toluene or xylene, a halogenated hydrocarbon, e.g. chlorobenzene or chloro form, or dioxane, during the course of /2 to 2 hours.
- the precipitate which generally results is filtered oil and the filtrate is washed with water.
- the solvent is subsequently removed in a vacuum at a bath temperature of approximately 20 to 50 C.
- the residue is subsequently distilled 3 in a high vacuum or, in the case of compounds which cannot be distilled, is crystallized.
- process (a) it is possible to employ a second equivalent of an amine of Formula III as acid acceptor.
- an aqueous solution of the amine of Formula III may be employed, and this is added to the compound of Formula II.
- Process (a) may likewise be effected by reacting phosphorus oxychloride, phosphorus oxybrotnide, phosphorus 4 thiochloride or phosphorus thiobromide with an acetoacetic ester of Formula V, in which R and X have the above significance, in the presence of an acid acceptor and, without isolating the resulting compound of general Formula II, adding an equivalent amount of the compound of general Formula III, in the presence of an acid acceptor, to the reaction mixture.
- a compound of Formula V is added, generally at 10 to +50 C., to a compound of Formula IV, in an inert solvent, e.g. toluene 50 or chlorobenzene, or optionally without solvent, and an acid acceptor, e.g. triethylamine, is added dropwise to the mixture.
- an inert solvent e.g. toluene 50 or chlorobenzene, or optionally without solvent
- an acid acceptor e.g. triethylamine
- the compounds of Formula I may be characterized in the usual manner by their physical constants.
- a predominant amount of the compound of Formula I obtained in accordance with the processes of the invention has a cis configuration in the crotonic acid radical, only a small amount having a trans configuration.
- the composition of the stereoisomeric forms of the compounds of Formula I may be determined in known manner employing a NMR spectrum.
- the production of compounds of Formula II may be effected by reaction of a phosphorus oxychloride or oxybromide, or phosphorus thiochloride or thiobromide, with an acetoacetic ester of the above Formula V, in which R signifies a lower alkyl radical containing 1 to 5 carbon atoms and X signifies a hydrogen or chlorine atom, in the presence of an acid acceptor.
- the compounds of Formula I obtained in accordance with the processes of the invention may be used as intermediates for the production of valuable biocides, e.g.
- R R R X and Y have the above significance, and R is an alkyl group of 1 to 5 carbon atoms.
- the compounds VI are thus prepared by reaction of a compound 1 with an equivalent amount of an alcohol of Formula VII,
- R 011 VII wherein R, has the above significance, in the presence of an acid acceptor, such as described above.
- the compounds VI particularly those wherein the --CH is cis to the COOR are useful insecticidal and acaracidal agents as indicated by their insecticidal effect against Bruchidius obtectus (bean Weevil) Alphis fabae (black bean aphid) Dysdercus fasciatus sign (red bug) and Aphis fabea and their acaracidal elfect against Tetranychus telarius (spider mite) in standard contact and systematic tests.
- a compound of Formula VI may be employed in the form of a dusting or spraying agent, e.g. as a solution or dispersion in water or a suitable organic solvent, e.g. alcohol, petroleum, tar distillates etc., and preferably in combination with an emulsifying agent, e.g.
- liquid polyglycol ether derived from a high molecular weight alcohol, mercaptan or alkylphenol and an alkylene oxide.
- Suitable organic solvents e.g. ketones, aromatic, optionally halogenated hydrocarbons, mineral oils etc., may also be added to the mixture as solution aids.
- the spraying and dusting agents may contain the usual inert carrier materials, e.g. talc, diatomaceous earth, bentonite, pumice, cellulose derivatives and the like, and the usual adhesives and wetting agents to improve adhesiveness and wettability.
- inert carrier materials e.g. talc, diatomaceous earth, bentonite, pumice, cellulose derivatives and the like
- adhesives and wetting agents to improve adhesiveness and wettability.
- the active material may be present in the formulations as a mixture with other known active agents.
- Formulations suitable for use in the application of a compound of Formula VI to a locus generally contain between 0.01 and 90 percent, and preferably between 0.1 and 20% by weight of active agent depending upon the method of application. Concentrates suitably contain between about 2% and 90% and preferably between 5% and 50% by weight of active ingredient.
- the ratio cis:trans isomer (in the crotonic acid radical) amounts to :10 (determined by the NMR spectrum).
- a mixture of 51.5 g, (0.25 mol) of N,N-diethyl-phosphoramido-thioate-dichloride and 29 g. (0.25 mol) of acetoacetic and acid methyl ester is added at 20 during the course of 3 hours to 25.5 g. (0.25 mol) of triethylamine.
- the reaction mixture is subsequently stirred at 20 for 10 hours and at 40 for 90 hours.
- the resulting precipitate is subsequently filtered oil, the filtrate is washed with water and dried with magnesium sulphate.
- EXAMPLE 5 Production of -(1methoxycarbonyl-l-chloro-l-propen- 2-yl)-N-n-propyl phosphoramido chloride-thionate (process b) A mixture of 48 g. (0.25 mol) of N-n-propylphosphoramidothioate-dichloride and 37.8 g. (0.25 mol) of u-chloro-acetoacetic acid methyl ester in 150 cc. of toluene is added to 25.5 g. of triethylamine at during the course of one hour. The reaction solution is subsequently stirred at 0 for one hour and at 20 for 15 hours.
- the precipitated triethylamine hydrochloride is subsequently filtered 011, the filtrate is washed with Water, dried with sodium sulphate, the solvent is removed by evaporation and the residue is distilled.
- EXAMPLE 7 Production of O-(l-iso-propoxycarbonyl-1-propen-2-yl)- N-ethyl-phosphoramido-chlorido-thionate (process a, in the presence of water) 12.8 g. of a 70% solution of ethylamine in water (0.2 mol) are added dropwise at 3 to 27.7 g. (0.1 mol) of O-(iso-propoxycarbonyl-1-propen-2 yl) phosphoro dichloridate during the course of 15 minutes while stirring. The mixture is stirred for a further 15 minutes, the oily product is separated, the residue is digested with water, dried and distilled in a high vacuum.
- O-(l-iso-propoxycarbonyl-l-propen-Z-yl)-N-ethyl phosphoramido chloridothionate has a boiling point of 89/5- 10* mm. of Hg. It has a refractive index of n 1.5 100.
- R is hydrogen, R is ethyl, R is methyl, X is hydrogen, and Y is oxygen.
- R is hydrogen, R is i-propyl, R is methyl, X is hydrogen, and Y is oxygen.
- R is hydrogen, R is n-propyl, R is ethyl, X is hydrogen, and Y is oxygen.
- R is hydrogen, R is n-propyl, R is i-propyl, X is hydrogen, and Y is oxygen.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH683669A CH519521A (de) | 1969-05-05 | 1969-05-05 | Verfahren zur Herstellung neuer Phosphorsäureamidohalogenide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3649719A true US3649719A (en) | 1972-03-14 |
Family
ID=4315783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US33862A Expired - Lifetime US3649719A (en) | 1969-05-05 | 1970-05-01 | Phosphoric acid ester amidohalides |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US3649719A (de) |
| JP (1) | JPS4819300B1 (de) |
| BE (1) | BE749921A (de) |
| CH (1) | CH519521A (de) |
| DE (1) | DE2021728A1 (de) |
| FR (1) | FR2047152A5 (de) |
| GB (1) | GB1306093A (de) |
| IL (1) | IL34446A (de) |
| NL (1) | NL7005997A (de) |
| ZA (1) | ZA703038B (de) |
-
1969
- 1969-05-05 CH CH683669A patent/CH519521A/de not_active IP Right Cessation
-
1970
- 1970-04-20 GB GB1867670A patent/GB1306093A/en not_active Expired
- 1970-04-24 NL NL7005997A patent/NL7005997A/xx unknown
- 1970-04-30 FR FR7015903A patent/FR2047152A5/fr not_active Expired
- 1970-05-01 US US33862A patent/US3649719A/en not_active Expired - Lifetime
- 1970-05-04 BE BE749921D patent/BE749921A/xx unknown
- 1970-05-04 IL IL34446A patent/IL34446A/xx unknown
- 1970-05-04 JP JP45038173A patent/JPS4819300B1/ja active Pending
- 1970-05-04 DE DE19702021728 patent/DE2021728A1/de active Pending
- 1970-05-05 ZA ZA703038A patent/ZA703038B/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IL34446A0 (en) | 1970-07-19 |
| DE2021728A1 (de) | 1970-11-19 |
| NL7005997A (de) | 1970-11-09 |
| GB1306093A (de) | 1973-02-07 |
| JPS4819300B1 (de) | 1973-06-12 |
| IL34446A (en) | 1973-03-30 |
| CH519521A (de) | 1972-02-29 |
| FR2047152A5 (de) | 1971-03-12 |
| ZA703038B (en) | 1971-12-29 |
| BE749921A (fr) | 1970-11-04 |
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